Among the two-dimensional (2D) materials family, layered double hydroxides (LDHs) represent a key member due to their unparalleled chemical versatility. In particular, Fe-based LDHs are distinguished candidates due to their high efficiency as oxygen evolution reaction (OER) electrocatalysts. Herein, we have selected MgFe-based LDH phases as model systems in order to decipher whether Fe-clustering exerts an effect on the OER performance. For that, we have optimized hydrothermal synthesis by using triethanolamine (TEA) as the chelating agent. The magnetic characterisation allows us to identify the Fe-clustering degree by following both magnetic susceptibility as well as magnetization values at 2 K. Thanks to this, we demonstrated that TEA induces an increment in Fe-clustering. Electrochemical OER measurements show that both samples behave identically by using glassy carbon electrodes. Interestingly, when the samples are tested in the most commonly employed electrode, nickel foam, striking differences arise. The sample exhibiting a lower Fe-clustering behaves as a better electrocatalyst with a reduction of the overpotential values of more than 50 mV to reach 100 mA cm−2, as a consequence of a favoured surface transformation of MgFe-LDHs phases into more reactive oxyhydroxide NiFe-based phases during the electrochemical tests. Hence, this work alerts about the importance of the electrocatalyst-electrode collector interactions which can induce misinterpretations in the OER performance.